Production of gi



Patented Apr-23, 1 2,198,367-

PRODUCTION OF GLYCIDE NITRATE Helmut Jacobi and Walter Flemming, Ludwigshafen-on-the-Rhine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany No Drawing. Application December 16, 1938, Se-

rial No. 246,074. In Germany December 30, 1937 3 Claims. (01. 260348) The present invention relates to the production monochlorhydrin mono-nitrate may be added in of glycide. nitrate, a compound corresponding to batches to the alkaline solution.

the formula It is not necessary for the monochlorhydrin CH2 CH CH2ONO2 mononitrate used as initial material to be pure, i but solutions in which it has been prepared may 5 also be directly used. Thus for example it is k preferable to carry out the preparation of glycide z g i g 3 3 52 giggi g nitrate according to this invention in direct con- I junction with the preparation of monochlorhythan. ntertainingaare from t m acid ester roup attached to a terminal carbon acld according to our copendmg apphcatmn atom) in the liquid phase with agents having is 3 7 filed g f t 1938' t an alkaline reaction. c or y rm mononi ra e is pro need by causing a u ous itri 1 Alkaline agents especially suitable for the req 6 n C and havmg speclfic gravlty above 1.1 to act in the cold on epichlorhydrin. Preaction are in particular alkali metal hydroxides Sumably the compound and carPonates sodium hydroxid? sodium CI-IzONO2 is formed in preponderating carbonate and bicarbonate, and alkaline earth amounts. In any event the nitric acid ester metal hydroxides; other alkaline agents, as for group is attached to a terminal carbon atom.

0 example ammonia, are, however, also suitable. Since according the Structure of mono The reaction is preferably carried out by treating chlorhydrin monomtrate, the ethylene oxide ring the monochlorhydrin mononitrate with a solution may be f ed by the Splitting ff of either of the alkaline agent When using strong drogen chloride or nitric acid, it is surprising Rallies, as for eXample high Percentage aqueous that glycide nitrate is mainly formed in the re- 5 alkali metal hydroxide solutions, it is usually unaction and that epichlorhydrin is formed only t necessary and in fact inadvisable 130' heat; the a subordinate degree The saponification of the latter s preferable when using more dilute nitric acid ester group with the formation of a hall metal hydroxide solutions or solutions of alhydroxyl group leading to glycerine, which would kah metal carbonates or alkaline earth metal have been expected 1 does not t place 0 hydroxides- Water preferably Serves as the The following examples will further illustrate Sol ent, wherein the Starting material mOIlO- how the said invention may be carried out in chlorhydlin monollitl'ate is; Soluble, but wherein practice but the invention is not restricted to the reaction product glycide nitrate is difiicultly these. examples The parts are by Weight. soluble. It is, therefore, especially advantageous 5 to work up aqueous reaction mixtures, because E$ample 1 the glycide nitrate readily separates therefrom 20 parts of monochlorhydrin mononitrate are as an oily layer. It may be purified by extractslowly added to 110 parts of a boiling 10 per cent ing it with organic solvents or by distillation or solution of sodium carbonate While stirring well. steam distillation. When carrying out the re The vapors formed are distilled through a cooler,

D action in organic solvents care should be taken care being taken by the addition of Water to 40 that such solvents are selected as do not react the reaction mixture that the water content of with the chlorine atom of the monochlorhydrin the solution remains approximately constant. mononitrate, such as is the case for example A good yield of glycide nitrate, which is difliculty with alcohols. soluble in water, separates from the aqueous dis- 5 The amount calculated on the hydrogen chlotillate inv the form of a heavy oil.

ride content of monochlorhydrin mononitrate or E l 2 a slight excess of the solution of the alkaline subxamp e stance may be added at once to monochlorhydrin 20 parts of monochlorhydrin mononitrate are mononitrate, or it may be added in batches or suspended in parts of water with powerful D slowly in a continuous manner at about the rate stirring. 6 parts of 15 per cent sodium car- 50 at which the splitting off of hydrogen chloride bonate solution are then introduced and the mixprogresses, care being taken that the reaction ture slowly heated to boiling. The vapors are mixture does not become acid, in other Words liquefied in a condenser. Corresponding to the that no free hydrogen chloride or nitric acid amount of water distilled ofi, a further parts 5 occurs in the reaction mixture. Conversely, of 15 per cent sodium carbonate solution are '5 added, are; being taken that the reaction mixture always has a weak alkaline reaction. The

oil driven over with the steam constitutes glycide nitrate. It collects at the bottom of the receiver and may readily be separated from the supernatant Water andpurified by distillation.

. Example 3 mononitrate, containing the nitric acid ester group attached to a terminal carbon atom, in the liquid phase with agents having analkaline action, while maintaining a neutral to alkaline reaction.

. 2. A process for the productionof glycide nitrate which comprises treating monochlorhydrin mononitrate, containing the nitric acid ester group attached to a terminal carbon atom, with aqueous solutionsof agents having an alkaline action, while maintaining a neutral to alkaline reaction.

3. A process for the production of glycide nitrate which comprises subjecting to distillation a mixture of monochlorhydrin mononitrate, containing the nitric acid ester group attached to a terminal carbon atom, and an aqueous sodium carbonate solution, the sodium carbonate content of which is at least equivalent to the monochlorhydrin mononitrate, condensing the vapors and separating the non-aqueous layer.

I I HELMUT JACOBI.

WALTER FLEMMING. 

